Vinyl polymers



Patented July so, 1946 2,404,191 ICE VINYL POLYMERS Donald D. Coiiman and Frank C.

mington, DcL.

McGrcw, Wilaasignors to E. I. du Pont de Ncmours a Company, Wilmington, Dei., a corporation of Delaware No Drawing. Application January Serial No. 421,940

4 Claims. (c1. zoo-as) This invention relates to vinyl polymers and more particularly to a new process for obtaining them. Many methods for the polymerization of vinyl compounds are known, but none is entirely satisfactory. The polymerization 01' vinyl halides presents special difllculties apparently due to the relative sluggishness oi the monomers in polymerization reactions. For example, although vinyl chloride can be polymerized more rapidly in emulsion than in any other physical state, the most eflective systems known heretofore, produce only very slow polymerization at moderate temperatures such as up to 45 C. It is not feasible to overcome this difliculty by increased temperatures, since the most suitable products, for many purposes, are those which are prepared at 45 C. or below. As a consequence, vinyl chloride polymerization by the methods or the art is limited in practice to a slow, uneconomical process which cannot be applied efliiciently to production on a large scale.

This invention has as its object to provide a method for polymerizing vinyl halides with extreme rapidity. Another object is to provide a practical and eflicient process for the extremely rapid polymerization of vinyl chloride at moderate temperatures. Still another object is to provide a practical and efiicient process for the copolymerization of vinyl halides with other substances capable of polymerization at an extremely rapid rate. Another object is toprovide a method of vinyl halide polymerization in which polymerization catalysts insoluble in organic media could be used with maximum effectiveness. Other objects will be apparent from the following description of the invention.

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These objects are accomplished by the following invention which comprise polymerizing the polymerizable components of an emulsion of a vinyl halide either alone or in admixture with, at least, one polymerizable unsaturated compound in an aqueous medium having pH of at least about 10, and containing a dissolved salt or perdisulfuric acid and a dispersing agent selected from the group consisting of aos o and sso OM OM wherein R is an acyclic hydrocarbon of 12 to 18 carbon atoms and M is an alkali metal. said polymerization being carried out with an oxygen-free atmosphere over said emulsion.

The exact manner of practicing this invention will vary depending upon the compounds poly- 2 persing agent such as a long chain primary alcohol sulfate or sulionate is adjusted to a pH of 10.5 by the addition of dilute caustic. This medium is then placed in a pressure vessel capable of withstanding the pressures developed by heating vinyl chloride (ca. 5-10 atmospheres). followed by about one-half its weight of vinyl are chilled below the boiling point of vi 1 chloride. The vessel is then sealed and as i t ated at 45 C. until polymerization is complete as indicated by a nearly complete loss or internal pressure due to vinyl chloride. This usually re- The following examples, in which the parts are given by weight, further illustrate the practice oi. the invention and demonstate by several series of systematic comparisons, the critical importance of the elements of the invention in obtaining rapid polymerization.

EXAMPLE I A series of aqueous solutions are prepared which are identical in every respect except that each solution contains a different oxygenliberating compound. The proportion of the oxygen-liberating compounds used in the individual solutions (see Table I below) are such that the solutions contain equimolecular amounts, based on the oxygen-liberating capacity of the compounds. In addition to this component, each solution contains the following ingredients: Nine parts of a suli'onated mineral oil dispersing agent containing 30 to 35% active ingredient, which is essentially identical to that described in Example 111 of U. S. Patent No. 2,197,800, 180 parts of water, and sufiicient 5% potassium hydroxide solution to bring the solution to a pH of 10.5. as determined by a glass-electrode DH-meter. The quantity of alkali required varies according to the ingredients of the solution but is usually less than 5 parts. These solutions are then placed in a series of identical pressure vessels, each having a capacity of about 6 times the volume of the aqueous solution. The vessels are cooled to --50 C'., and about parts of vinyl chloride is introduced into each. Air is removed from the containers by thorough flushing with nitrogen. Each is then sealed and connected to a shaking apparatus so devised that the vessels are immersed in a water bath maintained at a constant temperature of 45 C. After allowing 15 minutes for the temperature of the vessels and their contents to rise to 45 C., which produces an internal pressure of about 100 lbs/sq. in., the agitation is begun. The polymerization is arrested at the end of two hours by removing and open- 4 scribed inExample I. The yields or polymer present at theend of this time are tabulated in Table II as functions of the dlspersingagent and pH employed. The rapid polymerization attained by the use oi the selected class of dispersing agents of this invention contrast sharply with the lower polymerization rates produced by other agents. The critical importance oi the pH V or the aqueous phase is also evident from these data.

V Tssu II 5 Relative elllcacies of dispersing agent; and the influence of pH on the rapid emulsion polymerization vinyl chloride A momma Amount Yield of polyvinyl mouse 7,) obtained at various on a of active Dispersing agent, nature mated used,

parts pH pH pH pH pH H H H H B Wm 1.5 2.5 3.6 6.6 8.5 6.5 1%.0 1%.6 at 1%.6

Dispersing agents (ailing within the scope of this invention: I

Sodium hexadecyl-liiullateaiuiuifl.gfiau 100 3 69 45 89 90 '95 97 98 9o Sodiumsaltoreaconpr ucoce cohol 23:3 chorosuluionic a:d.i..i .1.. l g1 22 13 3 28 70 72 80 81- as ium toreaconrucooeygahol and clrorosulioni acid 33 9 3 9 I 3 g 87 59 65 Sodium salt of sulfonated white oil 9 40 56 47 e7 e9 7 g5 85 Sodium hexadecane-l-sulig nate. 100 3 i3 3 79 93 t idis rsing agen iid i salt i reection product of oleyl acemm and chlorosullonic acid 10 29 1 0 14 Sodium salt of reaction product of polymerizeg benzyl chloride and chlorosulionic m 6 28 o aci Sodium tetrahydronaphthalene sulionate 98 3 tt i it s-i is 2 g o v ny co 0 Tur l rey red-oil-.- 100 3 3 Team: I 36 EXAMPLE III Relative efllcacies of perdisulfates and other oxygen-liberating compounds as catalysts for emulsion polymerization of vinyl. chloride Equivalent Polyvinyl (b d n Parts chloride Promoter onset-bu used wigs, (pier 1 crating theory Perdisuliates:

Ammonium perdisuliate" 114 l. 02 85 Potassium perdisulfate- 135 1. 26 91 Sodium perdisulfate' 119 1. 06 93 Other oxygen-liberating col pounds:

Hydrogen peroxide 17 0.15 0 Benzoyl peroxide 121 l. 08 3 Sodium perborate monohydrate '50 0.45 3 Calcium peroxide 36 0.32 5 Dodecanoyl peroxide- I 199 l. 75 4 Ammonium perphosphate 139 1. 17 7 EXAMPLE II A" number of aqueous polymerization media are prepared, each comprising a solution of 1.02 parts of ammonium perdisulfate dissolved in 180 parts of water. In adding dispersing agent, the media Five identical polymerization mixtures are prepared and placed in pressure vessels as described withvinyl chloride vapor. One each of the prespH (in the range 1.5 to 12.5) as indicated in Table II. Each of these solutions, in an airfree, pressure vessel containing parts of vinyl chloride, is shaken for 2 hours at 45 C. as desure vessels is flushed with nitrogen, oxygen, and r methane, respectively, while the fifth is allowed to remain filled with air. The vessels are shaken at 10 C. for four hours and are then vented. The polymer yields obtained and the gases present are correlated in Table III. These results demonstrate that a tremendous acceleration of the polymerization rate is attained by the exclusion of atmospheric oxygen.

. TABLE III Comparison of operable andinoperable gaseous constituents of emulsion systems ,for the rapid .polymerization of vinyl chloride EXAMPLE IV A series of polymerization mixtures areintroduced into polymerization vessels. Each mixture comprises water parts), ammonium perdisulfate (1 part), sulfonated hydrocarbon dispersing agent referred to in Example I (9 parts), vinyl, chloride (85 parts); one of the interpolymerization ingredients listedin .Table IV below parts), and sufficient dilute hydrochloric acid to produce a pH of 2.5. A seco'ndseries of mixtures is prepared which is identical in every respect except that potassium hydroxide solution is added to bring each mixture to a pH of 10.5. The air in the polymerization vessels is then dis placed with nitrogen. The vessels are closed and shaken for two hours at 45 C. The yield of polymer produced in each mixture is given in Table IV. On the basis of these results, it is apparent that the high pH (10.5) promotes more rapid interpolymerization of vinyl chloride with other polymerizable compounds.

Tests IV Advantage of high pH in securing rapid interpolymerization .of ,m'nyl chloride with other polymerizable compounds The invention is generic to the polymerization.

of vinyl halides, especially vinyl fluoride, vinyl chloride, and vinyl bromide. Among these compounds vinyl chloride is polymerized most satisfactorily by the process of this invention, and is preferred. As indicated in Example IV, the process is also applicable to the polymerization of vinyl halides in the presence of other materials which contain one ethylenic bond capable of vinyl polymerization. This provides a uniquely effective means of obtaining interpolymers of vinyl halides with the following substances: Acrylic esters, including methyl and ethyl acrylates, chloroacrylic esters, methacrylic esters, especially methyl methacrylate, asymmetrical dichloroethylene, methyl vinyl ketone, acrylonitrile, methacrylonitrile, and fumaric and-maleic esters. The process of the present invention cannot be applied to interpolymerization mixtures containing vinyl esters of organic acids; these esters are so sensitive to alkaline hydrolysis that it is impossible to produce and maintain a pH of 10 or higher in their presence. With regard to interpolymerization, the invention is chiefly concerned with mixtures of polymerizable compounds which consist of at least 50% by weight of vinyl halides. In the preferred embodiment, vinyl halides comprise at least 80% of the mixture of materials to be polymerized.

The operability of the invention is not confined to any particular relation as regards proportion of vinyl compoundand proportion of aqueous media. For the most economical use of the accessory components, however, it is usually preferred to use an amount of vinyl compound of at least 1 6 the weight of the aqueous medium. It is also helpful in maintainingan emulsion if the proportion of organic to. greater than 1 :1 by weight.

As is self-evident from the description of the invention as an emulsion process, it is essential to have two immiscible phases, which must be aqueous phases is not intimately mixed in order to achieve rapid polymerization. An operable emulsion, in general, is

one in whicha plurality of the discreet portions of the organic material (1. e., droplets) are too' small to be seen with the naked eye. A satisfac tory emulsion may be secured in a number of ways. For example, many emulsions of, vinyl chloride in water are stable duringthe time required for polymerization, if the mixtures are initially agitated for a few minutes. The dispersing agents operable in this invention are in general especially useful in forming stable emulsions which, after they are once formed, need. not be agitated throughout the reaction. It has, how'- ever, been found that polymerization occurs more rapidly in certain emulsions while they are be; ing agitated. It isaccordingly preferred to assist the dispersing agent in maintaining the emulsion by mechanical means, for example, by stirring'or shaking, which may or may not be continuous.

As is evident from Example II, the pH of the aqueous medium is a critical factor in promoting rapid polymerization. It is to be noted especially that the rate of polymerization increases markedly between pH 9.5 and pH 10, and that the rates obtained if the pH is at least 10 are still more remarkably superior to those achieved in lower pH regions. This invention encompasses polymerizations carried out in systems having a pH of at least 10 and preferably below 12. Media having pHs considerably above 10 are to be avoided because of their effect upon the product. Thus, at pHs above 12, and particularlyabove 12.5, the caustic concentration is sufiiciently high to cause undesirable degradation of the polyvinyl chloride formed. It is believed that this degradation takes the form of abstraction of the elements of hydrogen chloride from the polymer molecules accompanied by partial neutralization 'of the alkaline hydroxide of the media, since the pH in such instances is observed to fall during the period Of contact of the polymer with the aqueous media. As a practical result of this phenomenon,

it is diificult to maintain a pH above 12 when polyerable, they are usually not employed because of their tendency to precipitate the corresponding alkalineearth hydroxide at high pHs. For these reasons, the preferred salts are the ammonium and alkali metal salts. Among them the alkali metal salts frequently produce somewhat superior results, while ammonium perdisulfate is preferred on account of its considerably lower cost.

The concentration of perdisulfate salt employed may be varied within wide limits. For instance, in proportions relative to the quantity of monomer employed, amounts of perdisulfate salts varying from 0.1% to 10% are operable. In respect to economy of catalyst, quality of product,

and rapidity of polymerization, the preferred salt lies in the range of proportion of perdisulfate 0.25 to 4% based on the weight of monomer,

As operable dispersing agents in addition to those disclosed in theforegoingexamples, there may be mentioned the alkali metal salts of the following long chain alkyl sulfates and sulioof this invention at nates: Dodecyl-l acid sulfate, tetradecyl-l acid sulfate, hexadecyl-l acid sulfate, octadecyl-l acid sulfate, oleyl-l acid sulfate, dodecane-l-sulfonic acid, tetradecane-l-sulfonic acid, hexadecanel-sulfonic acid and octadecane-l-sulfonic acid. The salts of long chain sulfonated paraffin ,oil hydrocarbons are especially effective dispersants and need be employed only in small proportions to achieve'the desired results. It will be understood that the dispersants to which reference is made above are commercial materials which, because of the methods used in their manufacture and because of the sources of the starting materials, are usually not produced in high state of purity and contain minor constituents which infiuence the effectiveness of the active ingredient. Polymerization systems containing such ancillary ingredients, which are present adventitiously or added deliberately, are recognized as part of this invention. These ingredients, which are useful only when an operable dispersant is also present,

may include inorganic salts, long chain primary alcohols, carbohydrate derivatives. polyvinyl alcohol, etc.

To a limited extent there is ag/irect relationship between the rate of polym ization and the quantity of dispersing agent present. Thus, while the outstanding superiority of the operable dispersing agents, as shown in Example II, is manifested in' aqueous concentrations of the active ingredient of about 1.5%, still more rapid polymerization can be efiected under otherwise identical conditions if the active dispersing agent ingredient is present to the extent of 3 to 5%. Conversely, it is observed that active ingredient concentrations (based on the weight of the aqueous phase) as low as 0.2% are associated with somewhat less rapid polymerization. Still lower concentrations of dispersing agent reduce the rate of polymerization considerably. Using the rate of polymerization as a criterion, the invention encompasses active ingredient concentrations of 0.2 to 5%. Within this range the preferred concentration will in general depend upon the proportion of monomer present, but is usually from 0.5 to 3%. For example, if an amount of monomer equal to the quantity of aqueous phase is employed, it will be most satisfactory to use the higher of the preferred dispersing agent concentrations. Conversely, if, for example, only this amount of monomer is present, the lower preferred concentration will be optimum. From the standpoint of economy and the ease of removing th dispersing agent from the polymerized product, it is customary to use approximately are not. Thus, with most of the inoperable dispersing agents, it is impossible to obtain the rapid rate of polymerization characteristic of the operable agents either by most vigorous agitation or.by the use of concentrations as high as the solubility of the material will permit. Even in instances where such modifications of systems involving inoperable dispersing agents permit sufficient acceleration of the polymerization rate,

- a the process is not practicable because of the expense and the operating dimculties entailed by the use of very high proportions of dispersing agent.

It is an essential element of this invention that the polymerization mixture be substantially free of gaseous oxygen. Specifically, it is necessary to reduce the oxygen content in the gas phase of the vessel employed to 1% or less. At oxygen contents below this point polymerization will proceed but is inhibited to an extent approximately proportional to the oxygen concentration. In order to achieve the rateof polymerization characteristic of this invention in its preferred form the oxygen content of the gas phase should be reduced to 0.1% or less. To this end-it is unnecessary that dissolved oxygen be removed from the liquid ingredients of the reaction mixture since the amount of oxygen involved is too small to be significant. It is important, however, to displace the air normally present in the gas phase with a non-inhibiting gas. This may be done in a number of ways as illustrated in Example III.

As is well known, the dependence of the rate of vinyl polymerization upon the temperature is very important, and low temperatures cannot usually be used because the corresponding rate of reaction is impracticably low. The present invention can be operated at any temperature above the freezing point of the aqueous phase which is somewhat below 0 C. Preferably, the polymerization is conducted at temperatures between 20 C., below which the reaction is too slow to be useful for most purposes, and C., above which the product is adversely affected by the medium.

The pressure employed in the process is usually that generated by vinyl chloride at the temperature employed. High'er pressures, such as may be obtained by forcibly introducing a gaseous diluent such as nitrogen, are also operable and in some cases desirable. The process is not limited to any particular apparatus. It is necessary only that a vessel be employed from which oxygen can be excluded which is able to withstand the pressures developed by the heated monomer. Various mechanical means may be used to mix the contents if mixing is desired. For example, the polymerization vessel may be shaken or tumbled. It is also possible and usually more satisfactory when operating on a large scale to mix the contents by means of a mechanical stirrer. In the operation of a continuous polymerization process,

the agitation is suitably provided by passing the ingredients through a centrifugal pump. The operating technique is not limited to the procedure used m the foregoing examples. For instance, instead of cooling the polymerization vessel before adding the ingredients, it is often equally suitable and sometimes preferred to introduce the monomer at the temperature at which polymerization is to be conducted. The monomer is thus usually introduced as a gas under pressure, and may be added continuously or' portionwise throughout the course of the reaction.

In addition to the necessary constituents of the polymerization mixture in this process as described in the foregoing, it is also possible to add other desired ingredients. For example, there may be introducedvarious substances which have the ability to soften, plasticize, or stabilize the final product.

The utility of the process of this invention centers in the remarkably rapid rate of polymerization which it produces. It is especially useful in effecting polymerization at a practicable rate ments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not to be limited to the specific embodiments shown and described.

We claim: V

1. A process for obtaining a resinous material which consists in emulsifying a vinyl halide in an aqueous medium wherein the ratio of aqueous to non-aqueous phase ranges from 10:1 to 1:1 by weight and having a pH within the range of 10 to 12, said medium containing from 0.1% to 10%, based on the weight of the vinyl halide, of a dissolved salt of perdisulfuric acid and from 0.2% to 5%, based on the weight of the aqueous phase, of a dispersing agent from the group consisting of o nos o and nszo \OM OM wherein R is an acyclic hydrocarbon of 12 to 18 carbon atoms and M is an alkali metal, and polymerizing the resulting emulsion at a temperature ranging from 0 C. to 80 C., while maintaining an inert, gaseous, oxygen-free atmosphere over said emulsion.

2. A process l'or obtaining aresinous material which consists in emulsifying vinyl chloride in an aqueous medium wherein the ratio of aqueous to non-aqueous phase ranges from 10:1 to 1:1 by weight and having a pH within the range of 10 to 12, said medium containing Irom 0.25% to 4%, based on the weight of the vinyl chloride, of a dissolved salt of perdisuliuric acid and from 0.2% to 5%, based on the weight of the aqueous phase, of a dispersing agent from the group consisting of wherein R is an acyclic hydrocarbon of 12 to 18 carbon atoms and M is an alkali metal, and po merizing the resulting emulsion at a temperature ranging from 20 C. to C., while maintaining an inert, gaseous, oxygen-free atmosphere over said emulsion.

3. The process, in accordance with claim 2 characterized in that the pH of the aqueous medium is about 10.5. a I

4. A process for obtaining a, resinous material which consists in emulsifying vinyl chloride in an aqueous medium. wherein the ratio of aqueous to non-aqueous phase is 1:1 by weight and having a pH within the range or 10-12, said medium containing from about 0.25%-4%, based on the weight of the vinyl chloride, of ammonium perdisulfate, and from 0.5%3%, based on the weight or the aqueous phase, of a salt of a long-chain alkyl sulionate as a dispersing agent, and then polymerizing the resulting emulsion by maintaining the same at a temperature ranging from about 20-80 0., while in contact with an atmosphere of nitrogen until polymerization becomes complete,

DONALD D. COFFMAN. FRANK C. McGREaW. 

